WO2021087769A1

WO2021087769A1 - Aqueous dispersion comprising polyurethane or polyurethane-urea, preparation method therefor and use thereof

Info

Publication number: WO2021087769A1
Application number: PCT/CN2019/115783
Authority: WO
Inventors: 宋泽峰; 孙永建; 纪学顺; 黎会亮; 张延成; 王远勇
Original assignee: 万华化学集团股份有限公司; 万华化学（宁波）有限公司; 万华化学（广东）有限公司
Priority date: 2019-11-05
Filing date: 2019-11-05
Publication date: 2021-05-14
Also published as: US20220363804A1; EP4026864A1; EP4026864A4

Abstract

Disclosed are an aqueous dispersion comprising polyurethane or polyurethane-urea, a preparation method therefor and a use thereof. The polyurethane or polyurethane-urea is prepared by reacting raw materials comprising the following components: (a) a compound having a tertiary amine group and at least one NCO reactive functional group, (b) a polyester polyol having a number average molecular weight of 400 to 5000 and a functionality of 2 to 3, (c) an organic compound having at least two isocyanate groups, (d) a hydrophilic compound having one or more of an ionic group, a potential ionic group and a non-ionic group and having 2 to 3 NCO reactive functional groups, and (e) a mono-functional non-ionic hydrophilic compound having at least one NCO reactive functional group. The aqueous dispersion can be stably stored for a prolonged period of time, and an adhesive prepared from the aqueous dispersion has an improved hydrolysis resistance while maintaining good bonding strength and heat resistance.

Description

A polyurethane or polyurethane-urea water dispersion and its preparation method and application

Technical field

The invention belongs to the technical field of polyurethane water dispersions, and in particular relates to a polyurethane or polyurethane-urea water dispersion and a preparation method and application thereof.

Background technique

Because polyurethane or polyurethane urea water dispersions have excellent paintability, excellent initial adhesion and peel strength, and outstanding resistance, they have been widely used in coatings, adhesives and textile coatings. When the water dispersion of polyurethane or polyurethane urea is used in the adhesive, in order to improve the performance of the adhesive, polyester polymer polyol is mainly used for synthesis. The ester polymer is in the process of processing, use and storage. The effect of water vapor and acidic substances in the environment will cause irreversible hydrolysis. The cracking and rupture of macromolecules caused by hydrolysis directly leads to the decrease of the tensile strength, modulus and hardness of the material and the increase of the elongation at break, which in turn reduces the bonding strength and leads to bonding failure. Therefore, how to efficiently and simply improve the water resistance of waterborne polyurethane or polyurethane urea has become an urgent problem for those skilled in the art.

Patent documents DE19954500, DE4410557 or EP792908 propose to introduce carboxylates into the water dispersion of polyurethane or polyurethane urea, and then compound with carbodiimide to improve the adhesion performance. This is mainly based on the use of carboxylic acid and carbon two The reaction of imines increases the cross-linking density and improves the strength of the adhesive. The carboxylate is obtained by adding dimethylolpropionic acid to the polyurethane or polyurethane urea and then neutralizing it with a tertiary amine. However, the reactivity of the carboxyl group and the carbodiimide in the compounding scheme of this type of binder is low, and the final performance is usually insufficient to meet the requirements of the binder for hydrolysis resistance at room temperature.

Patent document EP1272588 describes a kind of containing at least one crystalline polyester-polyurethane dispersion, polyacrylate copolymer, polychloroprene dispersion, heat curable resin and stabilizer (amino alcohol, carbodiimide and Magnesium oxide) adhesive compound, wherein the stabilizer used has the function of inhibiting the hydrolysis of the polyester in the system and maintaining the stability of the system. However, such a multi-component system is expensive and quick to fail, which severely limits its use in real life.

Patent document CN102216359 describes that by adding monoamino and/or monohydroxy carboxylic acid in the synthesis process, an aqueous dispersion of polyurethane or polyurethane urea containing carboxyl groups at the end is obtained, and then compounded with carbodiimide to form an adhesive ; Due to the high activity of the terminal carboxyl group, it can have a rapid cross-linking reaction with carbodiimide, thereby significantly improving the performance of the coating film. However, this carboxylic acid will affect the stability of the polyurethane or polyurethane urea aqueous dispersion, and the carbodiimide itself is not stable, which is not conducive to the storage of this system.

Patent document CN103980461 describes a method for synthesizing an aqueous dispersion containing epoxy resin crosslinking agent and 1-aminopropyl-2-methylimidazole, through the combination of 1-aminopropyl-2-methylimidazole and prepolymer -NCO group reaction can generate a covalent bond hybrid network structure, thereby forming a hybrid network structure. At the same time, epoxy resin is introduced to form a cross-linked structure, which improves the water resistance of the product. However, the use of cross-linking agent and the formation of the network structure will affect the activation of the product, which in turn affects the initial viscosity and strength of the product.

Patent document CN106634785 describes the preparation of a strong water-resistant waterborne polyurethane adhesive, which uses stearic acid, lipase and hydrogen peroxide to epoxy modification of cottonseed oil and castor oil, and then mixes it with KH-550 after modification. The modified oil can be obtained; the water-based polyurethane emulsion is modified by the modified oil to improve the water resistance of the product, and finally the modified water-based polyurethane emulsion is mixed with water-reducing agent, cross-linking agent and other substances to obtain water-resistant The water-based polyurethane adhesive. This method has complicated process steps, uses many raw materials, and does not use industrialized production and control. In addition, this patent uses more cross-linking agents, leading to deviations in other properties of the adhesive.

Although the above patent documents can improve the hydrolysis resistance to a certain extent, they all use a cross-linking agent to cross-link the polymer molecular properties. This type of method is not suitable for the use of activated products. Activation refers to: when the water dispersion is coated on the substrate, the water is removed by heating. At the same time, the mobility of the polyurethane segment increases at this temperature, and the polyurethane or polyurethane urea transforms into a viscoelastic state, and then Perform operations such as fitting. In polyurethane or polyurethane urea aqueous dispersions, the cross-linked structure reduces the mobility of the polyurethane segments, makes it insufficiently activated, and affects the initial adhesion, strength, and heat resistance.

Therefore, it is particularly important to explore hydrolysis-resistant polyurethane or polyurethane urea aqueous dispersions that will not affect the initial tack, strength, and heat resistance of the product during activation.

Summary of the invention

The purpose of the present invention is to provide a hydrolysis-resistant polyurethane or polyurethane-urea water solution in view of the problems in the prior art in the preparation of polyurethane or polyurethane-urea water dispersions using polyester polyols as raw materials to improve hydrolysis resistance. Dispersion and its preparation method and application. The side chain or main chain of the polyurethane or polyurethane-urea contained in the water dispersion contains tertiary amine groups (tertiary amine groups), which makes the water dispersion due to tertiary amine groups during storage. The amine group has strong basicity, which can eliminate acidic substances in the system, thereby eliminating the catalysis of acidic substances on ester polymers, greatly reducing the hydrolysis rate of ester polymers, and making the water dispersion stable in storage and storage time Long, it can greatly improve the hydrolysis resistance of the adhesive obtained from the dispersion, while maintaining the adhesive's good bonding strength and heat resistance.

In order to achieve the above objective, the technical solution of the present invention is as follows:

In one aspect of the present invention, there is provided a hydrolysis-resistant polyurethane or polyurethane-urea aqueous dispersion. The polyurethane or polyurethane-urea contained in the aqueous dispersion is prepared by reacting raw materials containing the following components:

a) A compound containing a tertiary amine group and at least one NCO reactive functional group,

b) A polyester polyol with a number average molecular weight of 400 to 5000 and a functionality of 2 to 3,

c) Organic compounds with at least two isocyanate groups,

d) Hydrophilic compounds containing one or more of ionic groups, potential ionic groups and nonionic groups and containing 2-3 NCO reactive functional groups,

e) a monofunctional nonionic hydrophilic compound containing at least one NCO reactive functional group,

f) Optionally, a compound containing 1 to 3 NCO reactive functional groups,

g) Optionally, blocking agents in the field of isocyanates or unsaturated compounds containing polymerization reactive groups.

According to the polyurethane or polyurethane-urea aqueous dispersion provided by the present invention, in some examples, based on the total weight amount of each component (for example, 100% by weight),

The amount of component a) is 0.02~5wt% (0.04wt%, 0.08wt%, 0.1wt%, 0.5wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.5wt%, 3.5wt%, 4wt%, 4.5wt%), preferably 0.05 to 3wt%;

The amount of component b) is 5-94wt% (8wt%, 15wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 65wt%, 74wt%, 76wt%, 80wt%, 85wt%), preferably 70～90wt%;

The amount of component c) is 5-40wt% (6wt%, 10wt%, 13wt%, 15wt%, 18wt%, 25wt%, 30wt%, 35wt%), preferably 8-20wt%;

The amount of component d) is 0.2-50wt% (0.4wt%, 0.8wt%, 1.5wt%, 2wt%, 4wt%, 8wt%, 15wt%, 20wt%, 30wt%, 40wt%), preferably 1 to 5wt%;

The amount of component e) is 0.01-20wt% (0.04wt%, 0.08wt%, 0.1wt%, 0.5wt%, 0.8wt%, 1wt%, 1.5wt%, 2wt%, 3.5wt%, 5wt%, 10wt% %, 15wt%), preferably 0.5-3wt%;

The amount of component f) is 0-10wt% (0.01wt%, 0.1wt%, 0.4wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3.5wt%, 5wt%, 8wt%), preferably 0.5～3wt%;

The amount of component g) is 0-15wt% (0.01wt%, 0.1wt%, 1wt%, 2wt%, 5wt%, 7wt%, 10wt%, 12wt%), preferably 0-8wt%.

Preferably, the polyurethane or polyurethane-urea contains a structural unit represented by formula (I):

Wherein, R is selected from component a) the residue after removing the NCO reactive functional group. For example, R can be N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldiethylenetriamine, N-methyldiethanolamine, N-ethyldiethanolamine, 1,4 -Bis(aminopropyl)piperazine, N-methylpiperazine, N-ethylpiperazine or N,N-dimethylethanolamine and other compounds are the residues after the NCO reactive functional group is removed. That is, these residues contain tertiary amine groups.

Preferably, the NCO reactive functional group is selected from _{one or more of primary amino group (-NH 2} ), secondary amino group (-NH-) and hydroxyl group (-OH).

Preferably, the component a) is selected from N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylenetriamine, N-methyldiethanolamine, N-ethyl One or more of diethanolamine, 1,4-bis(aminopropyl)piperazine, N-methylpiperazine, N-ethylpiperazine and N,N-dimethylethanolamine, more preferably selected from N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylenetriamine, N-methyldiethanolamine, N-ethyldiethanolamine and 1,4-bis(aminopropyl One or more of piperazine.

In the component b), suitable polyester polyols can be linear polyester diols or micro-branched polyester diols (containing a small amount of polyester polyols with a functionality greater than 3), for example, The known means consist of carboxylic acid or acid anhydride (such as aliphatic dicarboxylic acid or polycarboxylic acid, alicyclic dicarboxylic acid or polycarboxylic acid, aromatic dicarboxylic acid or polycarboxylic acid, or its corresponding anhydride, etc.) and Polyol is obtained through dehydration and condensation. Examples of carboxylic acids or anhydrides described herein include, but are not limited to, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid Acid, decane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, maleic acid, fumar Acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride, or mixtures thereof. Examples of polyols described herein include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3- Propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl- 1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-twelve Alkanediol or their mixture. Optionally, a higher functional polyol, for example, trimethylolpropane, glycerol, or pentaerythritol may be added in the process of preparing the polyester polyol.

The polyester polyols can also be homopolymers or copolymers of lactones, which can be obtained by ring-opening reaction of lactones or mixtures of lactones with suitable diols and/or higher-functional low-molecular-weight polyols. Suitable examples of the lactones described here include but are not limited to butyrolactone, ε-caprolactone, methyl-ε-caprolactone and their mixtures; the polyols described here preferably use 1,4- Butylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol and mixtures thereof.

In some examples, the component b) is selected from linear polyester diols with a number average molecular weight of 400 to 5000 and/or micro-branched polyester diols with a number average molecular weight of 400 to 5000.

In some examples, the component c) is selected from diisocyanates and/or polyisocyanates, preferably diisocyanates (its structural formula is Y(NCO) ₂ ). In the structural formula, Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms, a divalent aromatic hydrocarbon group containing 6-15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6-15 carbon atoms. A divalent araliphatic hydrocarbon group of 7-15 carbon atoms.

In addition to these simple diisocyanates, polyisocyanates having a functionality of more than 2 isocyanate groups per molecule are also suitable. For example, polyisocyanates prepared by simple modification of aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates or aromatic diisocyanates (e.g., carbodiimide groups, allophanate groups, Polyisocyanate modified by isocyanurate group, urethane group or biuret group), or polyisocyanate synthesized from at least two diisocyanates (synthetic polyisocyanate has uretdione, isocyanuric acid Ester, carbamate, allophanate, biuret, carbodiimide, iminooxadiazinedione or oxadiazinetrione structure).

The diisocyanate in component c) may be aliphatic diisocyanate and alicyclic diisocyanate, for example, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate and mixtures thereof. In a preferred embodiment, the diisocyanate is selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate , Isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-benzene diisocyanate, 2,4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate And one or more of p-xylylene diisocyanate; more preferably selected from 1,4-cyclohexane diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate One or more.

In some preferred embodiments, the component c) is a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate A mixture of acids. Among them, the mass ratio of hexamethylene diisocyanate and isophorone diisocyanate is 1-50:1, preferably 3-10:1; hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate The mass ratio of isocyanate is 1-50:1, preferably 3-10:1.

In the component d) of the present invention, the latent ion group contained refers to a functional group having a covalent bond. By adding a neutralizing agent to the reaction system, as the pH of the solution changes, the potential ion group is easily converted into a corresponding salt. The preferred potentially ionic group is an acid group selected from the group consisting of carboxyl -COOH and/or sulfonic acid -SO ₃ H.

The ionic groups contained include carboxylate -COO- and/or sulfonate -SO ₃ -.

The NCO reactive group contained is selected from hydroxyl (-COOH) and/or amino (for example, -NH ₂ , -NH-).

If a compound containing a potential ionic group is used as component d), a neutralizer can be added before, during or after the dispersion of the NCO-terminated polyurethane prepolymer obtained after the prepolymerization is completed, so that the potential ionic group can be eliminated. The regiment is neutralized. The amount of the neutralizing agent added is an amount that can partly or all of the potential ionic groups become ionic groups. Suitable neutralizing agents are, for example, one or more of primary amines, secondary amines, tertiary amines, alkali metal compounds and alkaline earth metal compounds; examples of suitable neutralizing agents include but are not limited to ammonia, ethanolamine, diethanolamine, Triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine , One or more of dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide. In general, sufficient neutralizing agent is added so that the degree of neutralization is at least 50%, preferably at least 75%, and not more than 150% based on the acid groups introduced. When the degree of neutralization exceeds 100%, in addition to 100% of the ionic salt groups, there are also free neutralizing amines. Particularly preferably, the degree of neutralization is 95 to 110%.

When a hydrophilic compound containing a nonionic group is used as the component d), examples of the hydrophilic compound containing a nonionic group include, but are not limited to, polyether diols, such as homopolymers of styrene oxide, oxides Styrene copolymer or styrene oxide graft product, ethylene oxide homopolymer, ethylene oxide copolymer or ethylene oxide graft product, propylene oxide homopolymer, propylene oxide copolymer or propylene oxide Grafted product, homopolymer of tetrahydrofuran, copolymer of tetrahydrofuran or grafted product of tetrahydrofuran, homopolymer of butylene oxide, copolymer of butylene oxide or grafted product of butylene oxide, homopolymer of epichlorohydrin Polyols, copolymers of epichlorohydrin or grafted products of epichlorohydrin, dehydration condensation products of polyols or their mixtures, and polyethers obtained by alkoxylation of diols, diamines and monoamino alcohols Dihydric alcohol. Among them, the number of ethylene oxide per molecule of the hydrophilic compound containing a nonionic group is 4 to 200, preferably 12 to 75.

The non-ionic group-containing hydrophilic compound can also be a multifunctional polyethoxy ether, such as pentaerythritol and sugar as the initiator, and the polymerization unit is one or two of propylene oxide and ethylene oxide. One is preferably ethylene oxide. Among them, the number of ethylene oxide per molecule is 4 to 200, preferably 12 to 75.

In some examples, the component d) is selected from hydrophilic compounds containing ionic groups and containing 2-3 NCO reactive functional groups, and hydrophilic compounds containing potential ionic groups and containing 2-3 NCO reactive functional groups And one or more of hydrophilic compounds containing non-ionic groups and containing 2-3 NCO reactive functional groups.

In a preferred embodiment, the hydrophilic compound containing an ionic group and containing 2-3 NCO reactive functional groups and/or the hydrophilic compound containing a potential ionic group containing 2-3 NCO reactive functional groups is selected from dihydroxy groups Carboxylic acid and its salt, trihydroxy carboxylic acid and its salt, dihydroxy sulfonic acid and its salt, trihydroxy sulfonic acid and its salt, diamino sulfonic acid and its salt, triamino sulfonic acid and its salt, diamino carboxylic acid One or more of its salts and triamino carboxylic acids and their salts; more preferably selected from dimethylol acetic acid and its alkali metal and/or ammonium salts, dimethylol propionic acid and its alkali metal salts And/or ammonium salt, dimethylolbutyric acid and its alkali metal salt and/or ammonium salt, dihydroxysuccinic acid and its alkali metal salt and/or ammonium salt, N-(2-aminoethyl)-2- Aminoethanesulfonic acid and its alkali metal salt and/or ammonium salt, N-(3-aminopropyl)-2-aminoethanesulfonic acid and its alkali metal salt and/or ammonium salt, N-(3-aminopropyl) Yl)-3-aminopropanesulfonic acid and its alkali metal salt and/or ammonium salt and one of N-(2-aminoethyl)-3-aminopropanesulfonic acid and its alkali metal salt and/or ammonium salt Or multiple.

In a preferred embodiment, the hydrophilic compound containing nonionic groups and containing 2-3 NCO reactive functional groups is a polyether glycol, more preferably a number average molecular weight of 200-8000 and the number of ethylene oxide It is a polyether diol of 4 to 200.

The component d) is more preferably selected from the group consisting of N-(2-aminoethyl)-2-aminoethanesulfonic acid alkali metal salt, ammonium dimethylolpropionate and Ymer ^{TM of Perstop (Perstop)} One or more of N-120. For example, component d) is sodium N-(2-aminoethyl)-2-aminoethanesulfonate.

The component e) of the present invention is a polyethoxy ether containing one hydroxyl group or one amino group (for example, -NH ₂ , -NH-). Examples of the initiator of the polyethoxy ether include, but are not limited to, saturated monohydric alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomer The pentanol, hexanol, octanol, nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, cyclohexanol, hydroxymethyl cyclohexane and 3-ethyl-3- Hydroxymethyl oxygen heterocycles), unsaturated alcohols (for example, allyl alcohol, 1,1-dimethyl-allyl alcohol or oleyl alcohol; aromatic alcohols such as phenol, isomerized cresol or hydroxymethyl phenol; aromatic Aliphatic alcohols such as benzyl alcohol, anisol or cinnamyl alcohol), secondary monoamines (e.g., dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, bis(2-ethylamine) Hexyl)-amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine), secondary heterocyclic amines (such as morpholine, pyrrolidine, piperidine ethyl pyrazole), etc.; preferably The starter is a saturated monohydric alcohol with up to 4 carbon atoms, and methanol is particularly preferred as the starter. The polymerization unit of the polyethoxy ether is propylene oxide and/or ethylene oxide, preferably ethylene oxide. Among them, the number of ethylene oxide per polyethoxy ether molecule is 4 to 200, preferably 12 to 75.

In some examples, the component e) is selected from monofunctional polyethoxy ethers having a number average molecular weight of 200 to 8000 and the number of ethylene oxides of 4 to 200, preferably selected from a number average molecular weight of 500 to 3000 and Polyethylene glycol monomethyl ether with 12 to 75 ethylene oxide.

The structural formula of polyethylene glycol monomethyl ether with an average molecular weight of 500-3000 and an ethylene oxide number of 12-75 is shown in formula (II):

In the formula, n=12～75.

In component f), the NCO reactive functional group is selected from _{one or more of hydroxyl, primary amino (-NH 2} ) and secondary amino (-NH-). In some examples, when component f) is a compound containing 2 to 3 NCO reactive functional groups, at least one of the NCO reactive functional groups is a primary amino group or a secondary amino group. Component f), for example, can be selected from aliphatic primary or secondary monoamines, alicyclic primary or secondary monoamines (e.g., ethylamine, diethylamine, isopropylamine, butylamine, cyclohexamine ); It can also be an amino alcohol, that is, a compound containing an amino group and a hydroxyl group in the molecule (for example, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N -(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine or 2-propanolamine); it can also be diamine and triamine, for example, 1,2-Ethylenediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), Piperazine, 1,4-diaminocyclohexane, bis-(4-aminocyclohexyl)methane, or diethylenetriamine. It can also be a special amine, for example, adipic acid dihydrazide and hydrazine. Mixtures of the aforementioned compounds can also be used. In a preferred embodiment, the component f) is selected from aliphatic primary monoamine, aliphatic secondary monoamine, alicyclic primary monoamine, alicyclic secondary monoamine, amino alcohol, aliphatic diamine, alicyclic One or more of aliphatic diamine, aliphatic triamine, alicyclic triamine and hydrazine, preferably selected from isophorone diamine, N-(2-hydroxyethyl) ethylene diamine and 1 , One or more of 6-hexamethylene diamine.

Component f) can act as a chain extender to achieve higher molecular weight, or as a monofunctional compound to limit molecular weight; or optionally also introduce other reactive groups, such as free hydroxyl groups, as other crosslinking points.

Component g) can be a blocking agent commonly used in the field of isocyanates (which can be removed at higher temperatures), for example, butanone oxime, dimethylpyrazole, caprolactam, malonate, triazole, dimethyl triazole Azole, tert-butylbenzylamine, cyclopentanone carboxyethyl ester; and unsaturated compounds containing polymerization reactive groups, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, methacrylic acid Hydroxybutyl ester, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate. Here, the blocking agent in the field of isocyanate refers to a substance used to block the monofunctional active hydrogen in the active isocyanate.

In a preferred embodiment, the component g) is selected from butanone oxime, dimethylpyrazole, caprolactam, malonate, triazole, dimethyltriazole, tert-butylbenzylamine, cyclopentanone carboxylate One or more of ethyl ester, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate Kind.

According to the polyurethane or polyurethane-urea aqueous dispersion provided by the present invention, in some examples, the polyurethane or polyurethane-urea aqueous dispersion has a solid content of 15 to 70 wt%, preferably a solid content of 30 to 60 wt%.

In some examples, the average particle size of the polyurethane or polyurethane-urea aqueous dispersion is 20-750 nm, preferably 50-450 nm.

Preferably, the pH of the polyurethane or polyurethane-urea aqueous dispersion is 7.5-11, more preferably 7.5-10, and still more preferably 7.5-8.5. The pH level is positively correlated with the content of tertiary amine groups in the water dispersion.

In another aspect of the present invention, there is provided a method for preparing the polyurethane or polyurethane-urea aqueous dispersion as described above, which comprises the following steps:

Component b), component c), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; the resulting polyurethane prepolymer is combined with component d ). Optional component f) undergoes a chain extension reaction, and then is dispersed in water or added to the mixture obtained after the chain extension reaction for dispersion to obtain an aqueous dispersion of polyurethane or polyurethane-urea; wherein, the group Component d) is a hydrophilic compound containing ionic or non-ionic groups and containing 2-3 NCO reactive functional groups; during the reaction, component a) can be added to the reaction system at any stage for reaction;

Alternatively, component b), component c), component d), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; make the resulting polyurethane The prepolymer is neutralized with the neutralizer, and then dispersed in water or added to the mixture obtained after the neutralization reaction for dispersion. The component a) is added for further reaction before, during or after the dispersion, An aqueous dispersion of polyurethane or polyurethane-urea is obtained; wherein the component d) is a hydrophilic compound containing a latent ion group and containing 2-3 NCO reactive functional groups.

In the preparation method of the present invention, after component a) is added to the system, no neutralization reaction is performed to ensure that the prepared polyurethane or polyurethane-urea contains tertiary amine groups.

According to the preparation method of the polyurethane or polyurethane-urea aqueous dispersion provided by the present invention, in some examples, the system can be diluted by adding a solvent, and the solvent can be partially or completely removed by distillation during or after the dispersion. For example, a water-miscible solvent that is inert to isocyanate groups may optionally be added for dilution during the reaction. Suitable solvents can be one or more of acetone, methyl isobutyl ketone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether and 1-methyl-2-pyrrolidone; they can not only It is added at the beginning of the preparation and can also be added during or after the polymerization reaction. It can also be added in batches. The solvent is preferably acetone and methyl ethyl ketone, more preferably acetone. Optionally used solvents, such as acetone, are distilled off during and/or after dispersion.

The preparation method can be carried out in a homogeneous phase in one or more stages, or partly in a dispersed phase in the case of a multistage reaction. The complete or partial polymerization reaction is followed by a dispersing, emulsifying or dissolving step. Optionally, addition polymerization or modification can be further carried out in the dispersed phase later.

In some examples, the component b), component c), component e) and optional component g) are mixed in one or more steps and then polymerized to form an isocyanate-terminated polyurethane prepolymer; The one-stage or two-stage reaction allows the obtained prepolymer to react with component a), component d) and optional component f), and then disperse the resultant product with water to obtain a polyurethane or polyurethane-urea aqueous dispersion .

In some examples, the polymerization reaction process is to pre-place all or part of the components b), d), e) and optional g) in the reactor, and optionally add water miscibility that is inert to isocyanate groups The solvent is diluted, and then the component c) is metered in between room temperature and 120° C. for prepolymerization to obtain an isocyanate-terminated polyurethane prepolymer. This reaction can be carried out in a single stage or in multiple stages.

A multi-stage reaction, for example, can be: pre-place component b), component c), component e) in the reactor and add component g) after reacting with a part of component c), which can then still exist with Another part of the component c) reaction, component a) can be added at any stage.

During the reaction, the conversion degree is usually monitored by tracking the NCO content of the reaction mixture. To this end, spectroscopic measurement (for example, infrared or near-infrared spectroscopy, determination of refractive index) and chemical potentiometric titration (for example, chemical titration by taking samples) can be used to achieve this, preferably chemical potentiometric titration.

During the reaction, a catalyst can optionally be added. The conventional catalyst may be a catalyst known to those of ordinary skill in the art for accelerating the reaction of -NCO and -OH. For example, triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, dibutyltin oxide, dioctoate, dibutyltin dilaurate, bis-(2-ethylhexyl) One or more of tin acid, bismuth neodecanoate and bismuth 2-ethylhexanoate. It is preferably bismuth neodecanoate or bismuth 2-ethylhexanoate, and more preferably bismuth neodecanoate.

During the reaction, the temperature in the chain extension reaction stage is usually 10-100°C, preferably 25-60°C.

In some preferred embodiments, the preparation method of polyurethane or polyurethane-urea aqueous dispersion is as follows: pre-add component b), component c), component e) and optional solvent in proportion to mix and heat to 50-100 ℃ while stirring. Using an exothermic reaction, the reaction mixture is stirred at 40-150°C until the theoretical isocyanate content has been reached or slightly lowered, optional component g) is added, and the reaction is continued to reach or slightly lower than the theoretical isocyanate content. Then it is diluted by adding solvent to a solid content of 25-95% by weight, preferably 40-80% by weight, and then at 10-100°C, preferably 25-60°C, component a) and component d) diluted with solvent are added respectively And optionally component f) undergoes chain extension. After a reaction time of 2 to 60 minutes, dispersion is carried out by adding distilled water or by transferring the mixture to distilled water placed in advance, and during or after the dispersion step, all or part of the solvent used is distilled off and some auxiliary agents are added afterwards. Agent (for example, emulsifier Tween 20). The polymerization reaction may optionally add a catalyst (for example, bismuth neodecanoate).

All methods known from the prior art, such as emulsifier shear, acetone, prepolymer mixing, melt emulsification, ketimine and solid spontaneous dispersion methods or their derivative methods, can be used in the present invention Preparation of polyurethane or polyurethane-urea aqueous dispersions. A review of these methods can be found in Methoden der organischen Chemie (Houben-Weyl, Erweiterungs-und

zur 4. Auflage, Volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pages 1671-1682). Preferably, a melt emulsification method, a prepolymer mixing method, and an acetone method are used. The acetone method is particularly preferably used.

In another aspect of the present invention, an application of the polyurethane or polyurethane-urea aqueous dispersion as described above or the polyurethane or polyurethane-urea aqueous dispersion obtained by the preparation method as described above in an adhesive is provided.

The polyurethane or polyurethane-urea aqueous dispersion prepared by the present invention can be used alone or together with known auxiliary substances and additives (in coating and adhesive technology). Commonly used auxiliary substances and additives, such as emulsifiers, light stabilizers (for example, UV absorbers and sterically hindered amines (HALS)), antioxidants, fillers, anti-settling agents, defoamers, wetting agents, flow regulators, Reactive diluents, plasticizers, neutralizers, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents, tackifiers, etc.

Auxiliary substances and additives can be added before or after polymerization. Of course, auxiliary substances and additives can also be added after dispersion.

It is also possible to mix the prepared polyurethane or polyurethane-urea aqueous dispersion with other water-containing or solvent-containing oligomers or polymers to improve the storage performance of the blended emulsion. These oligomers or polymers are, for example, polyvinyl ester, polyvinyl ether, polyvinyl alcohol, polyethylene, polystyrene, polybutadiene, polyvinyl chloride, polyurethane, polyurethane-polyurea, polyurethane-poly Acrylate, polyester, polyacrylate. Simple preliminary tests need to be used in each case to test the compatibility of such mixtures.

The prepared polyurethane or polyurethane-urea aqueous dispersion and the adhesive or adhesive composition based thereon are suitable for bonding any substrate. These substrates, for example, all types of metals, alloys, wood, wood-based materials, particle board, MDF boards, ceramics, stones, concrete, asphalt, hard fibers, glass, glass fibers, carbon fibers, carbon nanotubes, porcelain, leather, Textiles and inorganic materials, etc. They are also suitable for bonding rubber materials (for example, natural rubber and synthetic rubber), various plastics (for example, polyurethane, polyvinyl acetate, polyvinyl chloride, especially polyvinyl chloride containing plasticizers). They are also suitable for bonding thermoplastics, such as ABS (acrylic butadiene styrene), PC (polycarbonate), polyolefin plastics and their mixtures.

The prepared polyurethane or polyurethane-urea aqueous dispersion adhesive is also suitable for use in articles made therefrom. Examples of these products include, but are not limited to, shoe soles, such as soles based on polyvinyl chloride (especially polyvinyl chloride containing plasticizers), soles based on polyethylene vinyl acetate or polyurethane elastomer foam, and made of leather or artificial leather Adhesion of the finished shoe upper. It is also particularly suitable for bonding films based on polyvinyl chloride or polyvinyl chloride containing plasticizers with wood.

Compared with the prior art, the beneficial effects of the technical solution of the present invention lie in the following aspects:

In the aqueous dispersion obtained in the present invention, the side chain or main chain of the polyurethane or polyurethane-urea has a segment (ie, a tertiary amine group) contained in component a). In the storage process of the water dispersion, due to the strong basicity of the tertiary amine group, the acidic substance in the system can be eliminated, thereby eliminating the catalysis of the acidic substance on the ester polymer, so that the water dispersion can be stored stably . During the storage process, the tertiary amine group can eliminate the acidic substance in the system, greatly reduce the hydrolysis rate of the ester polymer, and can significantly improve the hydrolysis resistance of the adhesive obtained from the dispersion, while maintaining The adhesive has good bonding strength and heat resistance.

Compared with the existing waterborne polyurethane-polyurea water dispersion, the water dispersion of the present invention is used as a binder, and it has excellent hydrolysis resistance. The existing waterborne polyurethane-polyurea water dispersion is less than 6 Within -10 days (storage at 70°C), the hydrolysis resistance of the water dispersion of the present invention can reach 15-20 days (storage at 70°C).

The existing waterborne polyurethane-polyurea dispersions need to be added with crosslinking agents such as isocyanate or carbodiimide before use, and need to be mixed according to the ratio before construction. The operation is complicated, and the formulated adhesive must be used within the specified time. The open time is short, and the addition of the crosslinking agent also has a significant reduction effect on the initial viscosity of the adhesive; and the water dispersion of the present invention does not need to add additional crosslinking agents such as isocyanate or carbodiimide to meet performance requirements. It can be used as a one-component adhesive product with simple operation and long open time, which greatly increases construction efficiency.

Detailed ways

In order to be able to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein.

Polyester I: poly-1,4-butanediol adipate diol, OH value=56mg KOH/g(

WHP-204, Wanhua Chemical),

Polyester II: polyester diol composed of 1,6-hexanediol, neopentyl glycol and adipic acid, OH value = 74mg KOH/g(

WHP-1556, Wanhua Chemical),

Polyester III: Poly-1,4-butanediol adipate diol, OH value=112mg KOH/g(

WHP-104, Wanhua Chemical),

Polyester IV: Polyphthalate-1,6-hexanediol ester diol, OH value=56mg KOH/g (PH-56, Stepan),

Polyester V: polycarbonate diol, OH value = 56mg KOH/g (PCDL T5652, Asahi Kasei Corporation);

Isocyanate I: Hexamethylene diisocyanate (

HDI, Wanhua Chemical),

Isocyanate II: isophorone diisocyanate (

IPDI, Wanhua Chemical);

Polyether I: monofunctional polyethoxy ether with an average molecular weight of 1200g/mol (MPEG1200, LOTTE CHEM),

Polyether II: monofunctional polyethoxy ether with an average molecular weight of 520g/mol (MPEG520, LOTTE CHEM);

Bismuth neodecanoate (

Shepferd);

Sodium N-(2-aminoethyl)-2-aminoethanesulfonate (Vestamin A95, Evonik);

N-aminoethyl piperazine (Jinjin Lehua Science),

N,N-Dimethyldipropylenetriamine (Hengjingrui Chemical),

N-Ethyldiethanolamine (Hengjingrui Chemical);

Hydroxyethylethylenediamine, namely N-(2-hydroxyethyl)ethylenediamine (Yangtze BASF),

Isophorone diamine (Wanhua Chemical);

Butanone oxime (Jinjin Lehua Science);

Emulsifier Tween 20 (Shanghai Bangjing Industrial).

Measurement of average particle size of water dispersion: use Malvern particle size analyzer Nano S90 for testing.

Example 1

Put 210g of dehydrated polyester I, 29g of isocyanate I, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. The mixture was stirred at ~90°C until the NCO reached 2.09%. The obtained prepolymer was dissolved in 400 g of acetone and cooled to 50°C. Add 35g of an aqueous solution containing 4.63g of N-(2-aminoethyl)-2-aminoethanesulfonate, 2.47g of N-aminoethylpiperazine, and 1g of hydroxyethylethylenediamine to the dissolved prepolymer The acetone solution of the body was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 250 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.0.

Example 2

150g of dehydrated polyester I, 53g of dehydrated polyester II, 29g of isocyanate I, 24g of acetone, 0.04g of bismuth neodecanoate, and 2g of dehydrated polyether II were added to the 1L four In a round bottom flask, the mixture was stirred at 80 to 90°C until the NCO reached 1.94%. The obtained prepolymer was dissolved in 380 g of acetone and cooled to 50°C. Add 30g of aqueous solution containing 2g of N-(2-aminoethyl)-2-aminoethanesulfonate, 4g of N,N-dimethyldipropylenetriamine, and 1g of hydroxyethylethylenediamine to the dissolved The acetone solution of the prepolymer was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 210 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 55 wt% and an average particle diameter of 220 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.2.

Example 3

80g dehydrated polyester I, 33g dehydrated polyester III, 23g dehydrated polyester IV, 2g dehydrated polyether I, 22g isocyanate I, 18g acetone, 0.04g bismuth neodecanoate It was added to a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet, and the mixture was stirred at 80-90°C until the NCO reached 2.13%. The obtained prepolymer was dissolved in 309 g of acetone and cooled to 50°C. Add 4.6g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.5g of N,N-dimethyldipropylenetriamine, and 1g of hydroxyethylethylenediamine to 35g of aqueous solution. The acetone solution with prepolymer was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 224 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 45% by weight and an average particle diameter of 150 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.8.

Example 4

Add 60g of dehydrated polyester I, 77g of dehydrated polyester II, 35g of dehydrated polyester III, 29g of isocyanate I, 2g of dehydrated polyether I, 25g of acetone, and 0.04g of bismuth neodecanoate. Into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet, the mixture was stirred at 80-90°C until the NCO reached 2.05%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. A 35g aqueous solution containing 4g of N-(2-aminoethyl)-2-aminoethanesulfonate, 1g of isophoronediamine, 1.5g of N-aminoethylpiperazine, and 1g of hydroxyethylethylenediamine dissolved in it , Added to the acetone solution with prepolymer dissolved while stirring vigorously. Stir for 20 min, and then disperse the mixture by adding 238 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.7.

Example 5

Add 120g of dehydrated polyester I, 72g of dehydrated polyester II, 29g of isocyanate I, and 2g of dehydrated polyether I into a 1L four-neck round bottom flask equipped with nitrogen inlet and outlet. The mixture was stirred at °C until the NCO reached 2.15%. The obtained prepolymer was dissolved in 424 g of acetone and cooled to 50°C. Will dissolve 5g N-(2-aminoethyl)-2-aminoethanesulfonate sodium, 2g isophorone diamine, 1.2g N,N-dimethyldipropylene triamine, 1g hydroxyethyl ethylenediamine A 35 g aqueous solution of amine was added to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 20 min, the mixture was dispersed by adding 558 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 30% by weight and an average particle diameter of 164 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.7.

Example 6

Put 210g of dehydrated polyester I, 43g of isocyanate I, and 2g of dehydrated polyether I into a 1L four-neck round bottom flask equipped with nitrogen inlet and outlet, and stir the mixture at 80-90°C until NCO reaches 4.98% , Then add 15.2g of butanone oxime at 50°C, wait until the NCO is reduced to 2.20%. The obtained prepolymer was dissolved in 450 g of acetone and cooled to 50°C. Add 5g of N-(2-aminoethyl)-2-aminoethanesulfonate sodium, 4.5g of N-aminoethylpiperazine, 1g of hydroxyethylethylenediamine in 35g of water solution to the dissolved prepolymer While stirring vigorously in the acetone solution. Stir for 20 min, and then disperse the mixture by adding 253 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.3.

Example 7

Put 210g of dehydrated polyester I, 20g of isocyanate I, 11.1g of isocyanate II, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. , The mixture was stirred at 80-90°C until the NCO reached 1.98%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. Add 4.8g N-(2-aminoethyl)-2-aminoethanesulfonate sodium, 3g N-aminoethylpiperazine, 1g hydroxyethylethylenediamine in 35g aqueous solution to the dissolved prepolymer While stirring vigorously in the acetone solution. After stirring for 20 min, the mixture was dispersed by adding 241 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50 wt% and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.

Example 8

170g of dehydrated polyester I, 29g of isocyanate I, 4g of N-hydroxyethylpiperazine, 2g of dehydrated polyether I, 24g of acetone, and 0.02g of bismuth neodecanoate were added to 1L of bismuth with nitrogen inlet and outlet. In a round bottom flask, the mixture was stirred at 80-90°C until the NCO reached 2.05%. The obtained prepolymer was dissolved in 419 g of acetone and cooled to 50°C. Add 35g of an aqueous solution containing 4.5g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 2.5g of isophoronediamine, and 1g of hydroxyethylethylenediamine to the dissolved prepolymer While stirring vigorously in the acetone solution. Stir for 20 min, and then disperse the mixture by adding 300 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 40% by weight and an average particle diameter of 195 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.9.

Example 9

Add 210g of dehydrated polyester I, 32g of isocyanate I, 3g of N-ethyldiethanolamine, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate to a 1L four port equipped with nitrogen inlet and outlet. In a round bottom flask, the mixture was stirred at 80-90°C until the NCO reached 1.92%. The obtained prepolymer was dissolved in 413 g of acetone and cooled to 50°C. A 35 g aqueous solution in which 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate and 1 g of hydroxyethyl ethylenediamine are dissolved is added to the prepolymer-dissolved acetone solution while vigorously stirred. Stir for 20 min, and then disperse the mixture by adding 300 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 40% by weight and an average particle diameter of 195 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.

Example 10

Add 190g of dehydrated polyester I, 12g of dehydrated polyester V, 20g of isocyanate I, 11g of isocyanate II, 2g of dehydrated polyether I, 23g of acetone, and 0.04g of bismuth neodecanoate into the nitrogen inlet. In the outlet 1L four-necked round bottom flask, the mixture was stirred at 80-90°C until the NCO reached 2.15%. The obtained prepolymer was dissolved in 400 g of acetone and cooled to 50°C. Add 35g of an aqueous solution containing 4.63g of N-(2-aminoethyl)-2-aminoethanesulfonate, 3.2g of N-aminoethylpiperazine, and 1g of hydroxyethylethylenediamine to the dissolved prepolymer The acetone solution of the body was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 238 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 165 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.5.

Example 11

Add 190g of dehydrated polyester I, 20g of dehydrated polyester V, 20g of isocyanate I, 13g of isocyanate II, 2g of dehydrated polyether I, 23g of acetone, and 0.04g of bismuth neodecanoate to the nitrogen inlet. In the outlet 1L four-necked round bottom flask, the mixture was stirred at 80-90°C until the NCO reached 2.05%. The obtained prepolymer was dissolved in 400 g of acetone and cooled to 50°C. Add 35g of an aqueous solution containing 4.63g of N-(2-aminoethyl)-2-aminoethanesulfonate, 3.2g of N-aminoethylpiperazine, and 1g of hydroxyethylethylenediamine to the dissolved prepolymer The acetone solution of the body was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 238 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 178 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.3.

Example 12

80g dehydrated polyester I, 120g dehydrated polyester II, 30g dehydrated polyester III, 28.35g isocyanate I, 2g dehydrated polyether I, 25g acetone, 0.04g bismuth neodecanoate It was added to a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet, and the mixture was stirred at 80-90°C until the NCO reached 1.92%. The obtained prepolymer was dissolved in 395 g of acetone and cooled to 50°C. Add 35g aqueous solution in which 5g N-(2-aminoethyl)-2-aminoethanesulfonate sodium, 3g N,N-dimethyldipropylenetriamine, 1g hydroxyethylethylenediamine are dissolved The acetone solution of the prepolymer was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 238 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 185 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.

Example 13

Put 210g of dehydrated polyester I, 20g of isocyanate I, 11.1g of isocyanate II, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. , The mixture was stirred at 80-90°C until the NCO reached 1.98%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. Add 4.8g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 0.12g of N-aminoethylpiperazine, and 35g of hydroxyethylethylenediamine to 35g of water The acetone solution of the polymer was stirred vigorously at the same time. After stirring for 20 min, the mixture was dispersed by adding 241 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.2.

Example 14

Add 180g of dehydrated polyester I, 20g of isocyanate I, 11.1g of isocyanate II, 7g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. , The mixture was stirred at 80-90°C until the NCO reached 2.5%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. A 35 g aqueous solution in which 1 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate and 6.9 g of N-aminoethylpiperazine are dissolved is added to the prepolymer-dissolved acetone solution while stirring vigorously. After stirring for 20 min, the mixture was dispersed by adding 241 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.9.

Comparative example 1

Put 210g of dehydrated polyester I, 28.35g of isocyanate I, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. The mixture was stirred at 80-90°C until the NCO reached 1.72%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. Add 35g of an aqueous solution containing 5.1g of N-(2-aminoethyl)-2-aminoethanesulfonate, 3.51g of isophorone diamine, and 0.86g of hydroxyethyl ethylenediamine to the dissolved prepolymer The acetone solution of the body was stirred vigorously at the same time. Stir for 20 min, and then disperse the mixture by adding 300 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.0.

Comparative example 2

Put 210g of dehydrated polyester I, 20g of isocyanate I, 11.1g of isocyanate II, 2g of dehydrated polyether I, 24g of acetone, and 0.04g of bismuth neodecanoate into a 1L four-necked round bottom flask equipped with nitrogen inlet and outlet. , The mixture was stirred at 80-90°C until the NCO reached 1.98%. The obtained prepolymer was dissolved in 405 g of acetone and cooled to 50°C. Add 4.8g N-(2-aminoethyl)-2-aminoethanesulfonate sodium, 0.02g N-aminoethylpiperazine, 2.6g hydroxyethylethylenediamine dissolved 35g aqueous solution The acetone solution of the polymer was stirred vigorously at the same time. After stirring for 20 min, the mixture was dispersed by adding 241 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added. That is, a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.0.

The particle size and pH data of the polyurethane or polyurethane-urea aqueous dispersion prepared through each example show that we have successfully synthesized the PUD dispersion. Because in polyurethane or polyurethane-urea water dispersion containing tertiary amine group-introduced segment, the obvious change is the increase in pH value, and the pH value of the dispersion containing tertiary amine group is between 7.5-8.9, and The pH value of the dispersion without or with trace tertiary amine groups is basically 7.0.

The content of tertiary amine groups is very low compared to the entire polyurethane system and cannot be characterized by conventional spectroscopy. Because the tertiary amine group-containing component a) contains a group capable of reacting with NCO, and the NCO group is in excess, we believe that the tertiary amine group can be connected to the polyurethane or polyurethane urea molecular chain.

Preparation of adhesive

Mix 100g of the water dispersions obtained in each of the Examples and Comparative Examples with 0.05g BYK024 (BYK Chemicals), stir at 500rpm for 5min, then add 0.2g Tego245 (Tigao), stir for 5min, then add 0.15g Vesmody U604( Wanhua Chemical), and then stirred at 600 rpm for 10 minutes to obtain the respective adhesives corresponding to the respective examples and comparative examples.

Preparation and testing of test specimens

(1) Use the composite materials in Table 1 to prepare test samples:

复合材料Composite material	基材1Substrate 1	基材2Substrate 2
AA	橡胶rubber	橡胶rubber
BB	帆布canvas	帆布canvas
CC	PVCPVC	PVCPVC

First, the substrate 1 (rubber) and the substrate 2 (rubber) are polished. Then use a brush to thinly apply the prepared adhesive to a 2.5cm wide and 15cm long substrate strip and dry it in an oven at 65°C for 3 minutes, then take it out, and pass it through a hot press at 30kg/cm ² Under the conditions of pressing for 10 seconds, a composite material A was prepared.

Same as above, use the same method to prepare composite material B and composite material C.

(2) The peel strength of the composite material obtained by the test

The peel strength was measured with a GOTECH tensile machine at a peel rate of 200 mm/min. Among them, the initial strength: directly go to the tensile machine to test the peel strength after pressing. Later strength: After placing the specimen at room temperature for 24 hours, test its peel strength. The test results are shown in Table 2.

Table 2 Peel strength of each adhesive on different substrates

It can be seen from Table 2 that, compared to the one-component adhesive (Comparative Examples 1 and 2) obtained from the polyurethane water dispersion without or containing a trace (less than 0.02%) tertiary amine groups, the one-component adhesives (Comparative Examples 1 and 2) are prepared based on the present invention. Polyurethane or polyurethane-urea water dispersion one-component adhesive, its initial peel strength and later peel strength are equivalent, meet performance requirements, and do not affect normal use.

(3) Test the heat resistance of the composite material

Initial heat resistance: Hang the finished sample with a weight weighing 500 grams, place it in an oven at 80°C, and test the length of the sample being pulled out within 30 minutes.

Later heat resistance: After placing the finished sample at room temperature for 3 days, hang a weight of 1 kg and place it in an oven at 70°C to test the length of the sample being pulled out within 24 hours.

The test results are shown in Table 3.

Table 3 Heat resistance of each adhesive on different substrates

It can be seen from Table 3 that, compared to the one-component adhesives (Comparative Examples 1 and 2) obtained from polyurethane dispersions that do not contain or contain traces (less than 0.02%) of tertiary amine groups, those prepared based on the present invention The one-component adhesive of polyurethane or polyurethane-urea water dispersion has obvious improvement in initial heat resistance and later heat resistance.

(4) Test the hydrolysis resistance of polyurethane dispersion

If there is a hydrolysis reaction in the system, the molecular weight of the polyurethane or polyurethane urea segment will decrease, which in turn will cause the initial heat resistance of the substrate bonded with the water-based polyurethane or polyurethane urea as the adhesive to deteriorate. Therefore, the initial heat resistance value under high temperature/normal temperature conditions is used to characterize its hydrolysis resistance. The lower the initial heat resistance value, the better the hydrolysis resistance.

High temperature (70°C) hydrolysis resistance: Store the aqueous dispersions prepared in each example and comparative example at 70°C, respectively after 0 days, 3 days, 6 days, 9 days, 12 days, 15 days, 18 days and 21 days Take a sample and test the initial heat resistance level of the sample (using it as an adhesive) coated on the rubber substrate. The results of the high temperature hydrolysis resistance test are shown in Table 4.

Normal temperature (30°C) resistance to hydrolysis: Store the water dispersions prepared in the examples and comparative examples at 30°C for 0 days, 30 days, 60 days, 90 days, 120 days, 150 days, 180 days, and 210 days. A sample was taken after days to test the initial heat resistance level of the sample (using it as an adhesive) coated on the rubber substrate. The results of the hydrolysis resistance test at room temperature are shown in Table 5.

Table 4 After high temperature storage, the initial heat resistance of each adhesive on the rubber substrate

Table 5 After storage at room temperature, the initial heat resistance of each adhesive on the rubber substrate

It can be clearly seen from Table 4 and Table 5 that compared to the one-component adhesives (Comparative Examples 1 and 2) obtained from polyurethane dispersions that do not contain or contain a trace (less than 0.02%) tertiary amine groups (Comparative Examples 1 and 2), based on The one-component adhesive of polyurethane or polyurethane-urea aqueous dispersion prepared by the present invention has higher high temperature (70°C) hydrolysis resistance and normal temperature (for example, 25°C) hydrolysis resistance capabilities than those of Comparative Examples 1 and 2. This is because the side chain or main chain has the segment (ie, the segment containing the tertiary amine group) introduced by component a), which can react with the carboxylic acid present in the dispersion system, reduce the acid concentration in the system, and eliminate The catalyzed effect of carboxylic acid on the hydrolysis of ester groups, thereby reducing the hydrolysis of ester bonds in polyurethane or polyurethane urea polymers; the effect of hydrolysis resistance is reflected in the initial heat resistance test: as time goes by, the initial heat resistance drops extremely slow. The polyurethane dispersion prepared in Comparative Example 1 does not contain acid-eliminating structures or groups, and the irreversible ester group hydrolysis reaction will be accelerated due to the effect of acidic substances present in the system. Hydrolysis will cause cracks and breaks of macromolecules. The effect of hydrolysis resistance is reflected in the initial heat resistance test: as time goes by, the initial heat resistance drops rapidly. This shows that the water dispersion of polyurethane or polyurethane urea with tertiary amine group-containing segments in the side chain or main chain has excellent hydrolysis resistance. In addition, the content of the segment containing tertiary amine groups on the side chain or the main chain will also affect the hydrolysis resistance. For example, the adhesive obtained from the polyurethane dispersion of Example 10 has the best hydrolysis resistance; and Comparative Example 2 The hydrolysis resistance of the adhesive obtained by the polyurethane dispersion system is not as good as that of the examples.

The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Without departing from the scope and spirit of the described embodiments, many modifications and changes are obvious to those of ordinary skill in the art.

Claims

A hydrolysis-resistant polyurethane or polyurethane-urea aqueous dispersion, characterized in that the polyurethane or polyurethane-urea contained in the aqueous dispersion is prepared by reacting raw materials containing the following components:

a) A compound containing a tertiary amine group and at least one NCO reactive functional group,

b) A polyester polyol with a number average molecular weight of 400 to 5000 and a functionality of 2 to 3,

c) Organic compounds with at least two isocyanate groups,

d) Hydrophilic compounds containing one or more of ionic groups, potential ionic groups and nonionic groups and containing 2-3 NCO reactive functional groups,

e) a monofunctional nonionic hydrophilic compound containing at least one NCO reactive functional group,

f) Optionally, a compound containing 1 to 3 NCO reactive functional groups,

g) Optionally, blocking agents in the field of isocyanates or unsaturated compounds containing polymerization reactive groups.
The polyurethane or polyurethane-urea aqueous dispersion according to claim 1, characterized in that, based on the total weight of each component,

The amount of component a) is 0.02-5wt%, preferably 0.05-3wt%;

The amount of component b) is 5 to 94 wt%, preferably 70 to 90 wt%;

The amount of component c) is 5-40wt%, preferably 8-20wt%;

The amount of component d) is 0.2-50wt%, preferably 1-5wt%;

The amount of component e) is 0.01-20% by weight, preferably 0.5-3% by weight;

The amount of component f) is 0-10% by weight, preferably 0.5-3% by weight;

The amount of component g) is 0-15 wt%, preferably 0-8 wt%.
The polyurethane or polyurethane-urea aqueous dispersion according to claim 1 or 2, wherein the polyurethane or polyurethane-urea contains a structural unit represented by formula (I):

Wherein, R is selected from component a) the residue after removing the NCO reactive functional group.
The polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1 to 3, wherein the NCO reactive functional group is selected from one or more of primary amino group, secondary amino group and hydroxyl group.
The polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1 to 4, characterized in that:

The component a) is selected from N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylenetriamine, N-methyldiethanolamine, N-ethyldiethanolamine, One or more of 1,4-bis(aminopropyl)piperazine, N-methylpiperazine, N-ethylpiperazine and N,N-dimethylethanolamine, preferably selected from N-aminoethyl Piperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylene triamine, N-methyldiethanolamine, N-ethyldiethanolamine and 1,4-bis(aminopropyl)piperazine One or more of.
The polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1 to 5, wherein the component b) is selected from linear polyester diols with a number average molecular weight of 400 to 5000 and / Or a micro-branched polyester diol with a number average molecular weight of 400 to 5000; and/or

The component c) is selected from diisocyanates and/or polyisocyanates, preferably diisocyanates;

The diisocyanate is preferably selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone Diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate , 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate and p-xylylene diisocyanate One or more of diisocyanate; more preferably one or more selected from 1,4-cyclohexane diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate ；

The component c) is more preferably a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or a mixture of hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.
The polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1 to 6, characterized in that:

The component d) is selected from hydrophilic compounds containing ionic groups and containing 2-3 NCO reactive functional groups, hydrophilic compounds containing latent ionic groups and containing 2-3 NCO reactive functional groups, and hydrophilic compounds containing nonionic groups One or more of the hydrophilic compounds containing 2-3 NCO reactive functional groups;

Hydrophilic compounds containing ionic groups and containing 2-3 NCO reactive functional groups and/or hydrophilic compounds containing latent ionic groups and containing 2-3 NCO reactive functional groups are preferably selected from dihydroxycarboxylic acids and their salts , Trihydroxy carboxylic acid and its salt, dihydroxy sulfonic acid and its salt, trihydroxy sulfonic acid and its salt, diamino sulfonic acid and its salt, triamino sulfonic acid and its salt, diamino carboxylic acid and its salt and three One or more of amino carboxylic acid and its salt, more preferably selected from dimethylol acetic acid and its alkali metal salt and/or ammonium salt, dimethylol propionic acid and its alkali metal salt and/or ammonium salt , Dihydroxymethyl butyric acid and its alkali metal salt and/or ammonium salt, dihydroxysuccinic acid and its alkali metal salt and/or ammonium salt, N-(2-aminoethyl)-2-aminoethane sulfonic acid And its alkali metal salt and/or ammonium salt, N-(3-aminopropyl)-2-aminoethanesulfonic acid and its alkali metal salt and/or ammonium salt, N-(3-aminopropyl)-3- One or more of aminopropanesulfonic acid and its alkali metal salt and/or ammonium salt and N-(2-aminoethyl)-3-aminopropanesulfonic acid and its alkali metal salt and/or ammonium salt;

The hydrophilic compound containing non-ionic groups and containing 2-3 NCO reactive functional groups is preferably a polyether glycol, more preferably a number average molecular weight of 200 to 8000 and the number of ethylene oxide is 4 to 200 Polyether glycol;

The component d) is more preferably selected from the group consisting of N-(2-aminoethyl)-2-aminoethanesulfonic acid alkali metal salt, dimethylolpropionate ammonium salt and Perstorp’s Ymer TM N-120 One or more of; and/or

The component e) is selected from monofunctional polyethoxy ethers with a number average molecular weight of 200 to 8000 and the number of ethylene oxides from 4 to 200, preferably selected from a number average molecular weight of 500 to 3000 and ethylene oxide Polyethylene glycol monomethyl ether with a number of 12 to 75; and/or

The component f) is selected from aliphatic primary monoamine, aliphatic secondary monoamine, alicyclic primary monoamine, alicyclic secondary monoamine, amino alcohol, aliphatic diamine, alicyclic diamine, aliphatic One or more of triamine, alicyclic triamine and hydrazine, preferably selected from isophorone diamine, N-(2-hydroxyethyl) ethylene diamine and 1,6-hexamethylene One or more of diamines; and/or

The component g) is selected from butanone oxime, dimethylpyrazole, caprolactam, malonate, triazole, dimethyltriazole, tert-butyl benzylamine, cyclopentanone carboxyethyl ester, acrylic acid hydroxy One or more of ethyl ester, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate.
The polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1-7, wherein the polyurethane or polyurethane-urea aqueous dispersion has a solid content of 15 to 70 wt%, preferably 30 ～60wt% solid content;

The pH of the polyurethane or polyurethane-urea aqueous dispersion is 7.5-11, preferably 7.5-10, more preferably 7.5-8.5;

The average particle size of the polyurethane or polyurethane-urea aqueous dispersion is 20 to 750 nm, preferably 50 to 450 nm.
A preparation method of polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1-8, characterized in that it comprises the following steps:

Component b), component c), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; the resulting polyurethane prepolymer is combined with component d ). Optional component f) undergoes a chain extension reaction, and then is dispersed in water or added to the mixture obtained after the chain extension reaction for dispersion to obtain an aqueous dispersion of polyurethane or polyurethane-urea; wherein, the group Component d) is a hydrophilic compound containing ionic or non-ionic groups and containing 2-3 NCO reactive functional groups; during the reaction, component a) can be added to the reaction system at any stage for reaction;

Alternatively, component b), component c), component d), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; make the resulting polyurethane The prepolymer is neutralized with the neutralizer, and then dispersed in water or added to the mixture obtained after the neutralization reaction for dispersion. The component a) is added for further reaction before, during or after the dispersion, An aqueous dispersion of polyurethane or polyurethane-urea is obtained; wherein the component d) is a hydrophilic compound containing a latent ion group and containing 2-3 NCO reactive functional groups.
The application of the polyurethane or polyurethane-urea aqueous dispersion according to any one of claims 1-8 or the polyurethane or polyurethane-urea aqueous dispersion obtained by the preparation method according to claim 9 in an adhesive.